Dichloromethane
Pentane
[Rh(CO)₂Cl]₂  (ref 1)
[Ir(COD)Cl]₂ (ref 2)
P(4-biphenyl)₃ (ref 3)

trans-[Rh(P(4-biphenyl)₃)₂(CO)Cl] (1): A J. Young’s Flask was charged with [Rh(CO)₂Cl]₂ (30 mg, 0.077 mmol) and P(4-biphenyl)₃ (151 mg, 0.309 mmol), and CH₂Cl₂ (4 mL) added at room temperature. The reaction mixture was stirred for 5 minutes and the solvent removed in vacuo. The resulting yellow powder was washed with pentane (2 x 3 mL), to afford the pure product as yellow solid (Yield = 168 mg, 95%). Crystals suitable for X-Ray diffraction analysis were grown by slow diffusion of pentane into a CH₂Cl₂ solution.

trans-[Ir(P(4-biphenyl)₃)₂(CO)Cl] (2): A J. Young’s Flask was charged with [Ir(COD)₂Cl]₂ (150 mg, 0.223 mmol) and P(4-biphenyl)₃ (438 mg, 0.892 mmol), and CH₂Cl₂ (4 mL) added. The reaction mixture was freeze-pump-thaw degassed, placed under an atmosphere of CO and stirred for 5 minutes. The solvent removed in vacuo and the resulting yellow powder was washed with pentane (2 x 3 mL). Crystals suitable for X-Ray diffraction analysis were grown by slow diffusion of pentane into a CH₂Cl₂ solution (Yield = 453 mg, 82%).

All manipulations were performed under an atmosphere of nitrogen, using Schlenk and glove box techniques. Glassware was oven dried at 150ºC overnight and flamed under vacuum prior to use. Anhydrous CH₂Cl₂ and pentane were purchased and handled strictly under an inert atmosphere. CD₂Cl₂ was dried over CaH₂, vacuum distilled, and freeze-pump-thaw degassed three times before being placed under argon. Microanalyses were performed by Stephen Boyer at London Metropolitan University. Extreme caution is advised when using carbon monoxide gas: all manipulations and venting of CO should be carried within an efficient fumehood. Use of a personal gas detector is strongly advised.

[Rh(P(4-biphenyl)₃)₂(CO)Cl] (1)

¹H NMR (600 MHz, CD₂Cl₂) δ 7.90-7.95 (m, 12H), 7.72 (d, J_HH = 8.0, 12H), 7.67 (d, J_HH = 7.3, 12H), 7.47 (t, J_HH = 7.3, 12H), 7.39 (t, J_HH = 7.3, 6H). ¹³C{¹H} NMR (151 MHz, CD₂Cl₂) δ 187.4 (dt, J_RhC = 75, J_PC = 16) 143.5 (s), 140.6 (s), 135.7 (t, J_PC = 7), 132.3 (t, J_PC = 23), 129.4 (s), 128.5 (s), 127.7 (s), 127.4 (t, J_PC = 5). ³¹P{¹H} NMR (243 MHz, CD₂Cl₂) δ 27.8 (J_RhP = 126). Anal. Calcd for C₇₃H₅₄ClOP₂Rh (1147.51 gmol^-1): C, 76.41; H, 4.74. Found: C, 76.37; H, 4.82. IR (CH₂Cl₂, cm^-1): ν(CO) 1978. The solid-state structure of this compound has been deposited with the Cambridge Crystallographic Data Centre under CCDC 1498191. 

 [Ir(P(4-biphenyl)₃)₂(CO)Cl] (2)

¹H NMR (400 MHz, CD₂Cl₂) δ 7.94 (br d, J_HH = 7.8, 12H), 7.67-7.82 (m, 24H), 7.37-7.55 (m, 18H). ¹³C{¹H} NMR (101 MHz, CD₂Cl₂) δ 172.2 (t, J_PC = 11), 143.7 (s), 140.5 (s), 135.9 (t, J_PC = 6), 131.6 (t, J_PC = 27), 129.5 (s), 128.5 (s), 127.8 (s), 127.4 (t, J_PC = 5). ³¹P{¹H} NMR (122 MHz, CD₂Cl₂) δ 22.8. Anal. Calcd for C₇₃H₅₄ClOP₂Ir (1236.82 gmol^-1): C, 70.89; H, 4.40. Found: C, 71.01; H, 4.60. IR (CH₂Cl₂, cm^-1): ν(CO) 1965. The solid-state structure of this compound has been deposited with the Cambridge Crystallographic Data Centre under CCDC 1498192.

 

1. J. A. McCleverty, G. Wilkinson, L. G. Lipson, M. L. Maddox, H. D. Kaesz, Inorg. Synth. 1990, 28, 84–86.
http://dx.doi.org/10.1002/9780470132593.ch20
2. J. L. Herde, J. C. Lambert, C. V. Senoff, M. A. Cushing, Inorg. Synth. 1974, 15, 18–20.
http://dx.doi.org/10.1002/9780470132463.ch5
3. M. Joshaghani, E. Faramarzi, E. Rafiee, M. Daryanavard, J. Xiao, C. Baillie, J. Mol. Catal. A: Chem. 2006, 259, 35–40.
http://dx.doi.org/10.1016/j.molcata.2006.05.062